Shape selective reactions with zeolite catalyst modified with group IVB metal

• US 4,278,827 A
• Filed: 04/07/1980
• Issued: 07/14/1981
• Est. Priority Date: 04/07/1980
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Kaeding, Warren W., Chu, Chin-Chiun
• Primary Examiner(s): Davis, Curtis R.
• Application Number:
  US06/137,881
• Time in Patent Office: 463 Days
• Field of Search: 585/467, 585/474, 585/475, 585/470
• US Class Current: 585/467
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/65 of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: C07C 15/02 Monocyclic hydrocarbons
• CPC Class Codes: C07C 2/66 Catalytic processes
• CPC Class Codes: C07C 2/864 the non-hydrocarbon is an alcohol
• CPC Class Codes: C07C 2529/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: C07C 2529/65 of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
• CPC Class Codes: C07C 2529/70 of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: C07C 6/123 of only one hydrocarbon
• CPC Class Codes: C07C 6/126 of more than one hydrocarbon

Abstract

A process for the conversion of aromatic compounds to dialkylbenzene compounds rich in the 1,4-dialkylbenzene isomer. The reaction is carried out in the presence of a particular type of zeolite catalyst having a silica to alumina mole ratio of at least 12 and a constraint index of about 1-12, said catalyst having been modified by treatment with compounds of germanium, tin and/or lead, and optionally phosphorus, to deposit a minor proportion of such elements on the zeolite.

Claims

1. A process for conversion of organic compounds, said process comprising contacting said organic compounds with a crystalline zeolite catalyst at a temperature of between about 250°

C. and about 750°

C. and a pressure within the approximate range of 10⁵ N/m² to 10⁷ N/m², said zeolite being characterized by a silica to alumina mole ratio of at least 12 and a constraint index within the approximate range of 1 to 12, said zeolite having undergone prior modification by treatment with one or more compounds containing metal elements of Group IVB to deposit thereon at least 0.25 weight percent of such metal element.

2. The process of claim 1 wherein said temperature is between 300°

C. and 650°

C.

3. The process of claim 1 wherein said metal element of Group IVB is chosen from the group consisting of germanium, tin and lead.

4. The process of claim 1 wherein said metal element is germanium.

5. The process of claim 4 wherein said germanium comprises between 1 and 15 weight percent of the modified zeolite catalyst.

6. The process of claim 1 wherein said metal element is tin.

7. The process of claim 6 wherein said tin comprises between 1 and 25 weight percent of the modified zeolite catalyst.

8. The process of claim 1 wherein said metal element is lead.

9. The process of claim 8 wherein said lead comprises between about 1 and 40 weight percent of the modified zeolite catalyst.

10. The process of claim 1 wherein said zeolite is also modified by treatment thereof with a compound of the element phosphorus to deposit thereon at least 0.25 weight percent of phosphorus.

11. The process of claim 10 wherein said zeolite has deposited thereon both phosphorus and germanium.

12. The process of claim 10 wherein said zeolite has deposited thereon both phosphorus and tin.

13. The process of claim 10 wherein said zeolite has deposited thereon both phosphorus and lead.

14. The process of claim 1 wherein said zeolite is admixed with a binder therefor.

15. The process of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 wherein said conversion comprises the alkylation of an aromatic compound by contacting said compound with an alkylating agent to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration.

16. The process of claim 15 wherein said zeolite is chosen from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.

17. The process of claim 15 wherein said zeolite is ZSM-5.

18. The process of claim 15 wherein said zeolite is ZSM-11.

19. The process of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 wherein said conversion comprises the transalkylation of aromatic compounds to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration.

20. The process of claim 19 wherein said zeolite is chosen from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.

21. The process of claim 19 wherein said zeolite is ZSM-5.

22. The process of claim 19 wherein said zeolite is ZSM-11.

23. The process of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 wherein said conversion comprises disproportionation of alkylbenzenes to produce benzene and dialkylbenzenes in which the proportion of 1,4-dialkylbenzene isomer is in excess of its normal equilibrium concentration.

24. The process of claim 23 wherein said zeolite is chosen from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.

25. The process of claim 23 wherein said zeolite is ZSM-5.

26. The process of claim 23 wherein said zeolite is ZSM-11.